JP2015512141A - Method for forming a joint between magnesium diboride conductors - Google Patents
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Abstract
接合すべきワイヤからMgB2フィラメントを露出させるステップと、炉中でMgB2フィラメントをマグネシウム粉末およびホウ素粉末の混合物にさらすステップと、MgB2フィラメントならびにマグネシウムおよびホウ素粉末を一緒に540℃を超えるまたは540℃程度の温度で圧縮するステップとを含む、超伝導ワイヤのMgB2フィラメント間に接合部を形成するための方法。チタンが、炉内に提供されて、炉内に存在する酸素を優先的に捕捉する。Exposing the MgB2 filaments from the wires to be joined, exposing the MgB2 filaments to a mixture of magnesium and boron powders in a furnace, and the MgB2 filaments and the magnesium and boron powders together above 540 ° C. Compressing with temperature and forming a joint between MgB2 filaments of the superconducting wire. Titanium is provided in the furnace to preferentially capture oxygen present in the furnace.
Description
二ホウ化マグネシウム(MgB2)は、例えばMRIシステムなどの撮像システムのための超伝導磁石を製作するために使用されるワイヤ中のフィラメントのような超伝導体として使用される。 Magnesium diboride (MgB 2 ) is used as a superconductor, such as a filament in a wire used to fabricate a superconducting magnet for an imaging system such as an MRI system.
MgB2フィラメント間に十分な接合部を作ることは、困難であることが分かっている。接合部は、動作温度においてさえ超伝導にならないか、または接合部は、容認できないほど低い背景磁界強度においてもしくは容認できないほど低いしきいを超える電流が通されるときに抵抗性になる(「クエンチ現象」として知られている)。 Producing sufficient joints between MgB 2 filaments has proven difficult. The junction does not become superconducting even at operating temperatures, or the junction becomes resistive when a current is passed at an unacceptably low background magnetic field strength or above an unacceptably low threshold ("quenching" Known as "phenomenon").
MgB2接合部を形成するための典型的な周知のプロセスは、接合すべきワイヤからMgB2フィラメントを露出させるステップと、それらを一緒に圧縮するステップと、脱ガスのための真空下で、540℃を超えるまたは540℃程度の温度で炉中のモールド中でそれらをマグネシウム粉末およびホウ素粉末にさらすステップとを含む。粉末は、混合され、結果として得られるMgB2接合部の密度を最大にするために圧縮される。例えば、2〜30トンの重量が、粉末を圧縮するために使用されることもある。圧縮は、結果として得られる接合部が、接合部の有効性を低減することになる多孔性となるのを防止することを目指している。温度は、粉末が実際には溶融しないが、しかし効果的に圧縮できるように、マグネシウムまたはホウ素の溶融点をわずかに下回るように選択される。高温は、MgB2を生成するための反応が妥当な速度で続くことを確実にする。 A typical well-known process for forming the MgB 2 joint includes exposing the MgB 2 filaments from the wires to be joined, compressing them together, and under vacuum for degassing 540 Exposing them to magnesium and boron powders in a mold in a furnace at a temperature above or at about 540 ° C. The powder is mixed and compressed to maximize the density of the resulting MgB 2 joint. For example, a weight of 2 to 30 tons may be used to compress the powder. Compression seeks to prevent the resulting joint from becoming porous which will reduce the effectiveness of the joint. The temperature is selected to be slightly below the melting point of magnesium or boron so that the powder does not actually melt but can be effectively compressed. The high temperature ensures that the reaction to produce MgB 2 continues at a reasonable rate.
このプロセスは、フィラメントへのMgB2の堆積をもたらし、あるワイヤのフィラメントから他のワイヤのフィラメントへと、MgB2を含む接合部を提供する。別法では、圧力は、熱処理ステップの間維持されることもあり、または圧力は、いったん粉末が圧縮されると、熱処理ステップの前に解放されることもある。 This process results in the deposition of MgB 2 on the filament, providing a joint containing MgB 2 from one wire filament to another. Alternatively, the pressure may be maintained during the heat treatment step, or the pressure may be released prior to the heat treatment step once the powder is compressed.
そのような準備方法では、粉末は典型的には、約25μm直径の粒子でできている。熱処理ステップの間に、MgおよびBは、一緒に反応して、Mg粒子の表面に約2から5μmの厚さのMgB2の層を形成する。接合されたワイヤのMgB2フィラメント間の超伝導は、これらのMgB2の表面層を通じて起こる。圧縮ステップは、効果的な伝導経路を提供するために、粒子が密着することを確実にするために必要とされる。熱処理は、MgかまたはBの溶融点を下回る温度で、しかしMgB2を生成するための反応が妥当な速度で起こるのに十分な高い温度で行われる。 In such a preparation method, the powder is typically made of particles about 25 μm in diameter. During the heat treatment step, Mg and B react together to form a layer of MgB 2 about 2 to 5 μm thick on the surface of the Mg particles. Superconductivity between the MgB 2 filaments of the bonded wires occurs through these MgB 2 surface layers. A compression step is required to ensure that the particles are in close contact to provide an effective conduction path. The heat treatment is performed at a temperature below the melting point of either Mg or B, but high enough that the reaction to produce MgB 2 occurs at a reasonable rate.
典型的なMgB2超伝導ワイヤでは、いくつかのMgB2コアが、提供され、それぞれが、保護層、例えば鉄、またはニオブ、またはMONEL(登録商標)合金の層で被覆されている。被覆コアは次いで、MgB2コアでのクエンチの場合に機械的強度および代替電気経路を提供するために、銅ケーシング(copper outer)に入れられる。被覆は、MgB2コアが銅ケーシングと反応するのを防止するため、およびワイヤの製造の間コアに機械的強度を提供するために必要である。MgB2は、脆いことが周知であり、もし極端に曲げられるならば砕け散ることになる。 In a typical MgB 2 superconducting wire, several MgB 2 cores are provided, each coated with a protective layer, such as a layer of iron, or niobium, or a MONEL® alloy. The coated core is then placed in a copper outer to provide mechanical strength and an alternative electrical path in the case of a quench with the MgB 2 core. The coating is necessary to prevent the MgB 2 core from reacting with the copper casing and to provide mechanical strength to the core during wire manufacture. MgB 2 is well known to be brittle and will shatter if bent excessively.
従来の接合プロセスは、コアから保護層をはぎ取るステップを含んでいる。露出したコアは次いで、上で述べたように、接合のためにマグネシウムおよびホウ素粉末とともにモールド中に置かれる。別法として、保護層は、はぎ取られないが、しかしMgB2コアおよび保護層をそれぞれ含むフィラメントは、比較的大きい表面積にわたってコアを露出させるために、2°〜5°の角度などの浅い角度で切断され、または削られる。一例では、コアは、約40mmの長さにわたって露出されることもある。これらのフィラメントは次いで、上で述べたように、マグネシウムおよびホウ素粉末とともにモールド中に置かれる。 Conventional bonding processes include the step of stripping the protective layer from the core. The exposed core is then placed in a mold with magnesium and boron powder for bonding as described above. Alternatively, the protective layer is not stripped, but containing filaments MgB 2 core and the protective layer, respectively, to expose the core over a relatively large surface area, shallow angle such as an angle of 2 ° to 5 ° Is cut or shaved. In one example, the core may be exposed over a length of about 40 mm. These filaments are then placed in a mold with magnesium and boron powder as described above.
理論的に魅力的であるが、そのようなMgB2の持続的接合部は、実現するのが非常に困難であることが判明している。制限する要因の1つは、接合部の堆積されたMgB2中に見られる酸化マグネシウムの量である。酸化マグネシウムで汚染された接合部は、0Tの背景磁界であっても、持続的でない、すなわち超伝導でないことが分かっている。 While theoretically attractive, such MgB 2 persistent joints have proven very difficult to achieve. One limiting factor is the amount of magnesium oxide found in the deposited MgB 2 at the joint. It has been found that the junction contaminated with magnesium oxide is not persistent, i.e. not superconducting, even with a background magnetic field of 0T.
酸素は、プロセスで使用されるマグネシウム粉末に存在する酸化マグネシウムから、およびおそらくはまた炉それ自体の構造からも真空炉中に抜け出ると信じられている。酸化マグネシウムMgOは、本明細書で述べる方法に従ってMgB2形成を達成するために典型的に用いられる温度をはるかに下回る温度でマグネシウムおよび酸素に解離する。 It is believed that oxygen escapes into the vacuum furnace from the magnesium oxide present in the magnesium powder used in the process, and possibly also from the structure of the furnace itself. Magnesium oxide MgO dissociates into magnesium and oxygen at temperatures well below those typically used to achieve MgB 2 formation according to the methods described herein.
MgB2ワイヤを接合する従来の方法は、
− 接合すべきワイヤのそれぞれで少なくとも1つのMgB2フィラメントを露出させるステップと、
− 露出したMgB2フィラメントをモールド中に置くステップと、
− マグネシウムおよびホウ素粉末をモールド中に追加するステップと、
− モールド中の粉末を機械的に圧縮するステップと、
− フィラメントおよび粉末を熱処理して、接合されるワイヤのフィラメント間に延びるMgB2接合部を作成するステップとを含む。
Conventional methods of joining MgB 2 wires are:
- a step of exposing at least one MgB 2 filaments each be joined wires,
- a step of placing the MgB 2 filaments exposed into a mold,
-Adding magnesium and boron powder into the mold;
-Mechanically compressing the powder in the mold;
Heat treating the filaments and powder to create a MgB 2 joint extending between the filaments of the wires to be joined.
本発明は、この最終ステップに関する。熱処理ステップの間に、炉内のどんな遊離酸素も、マグネシウム粉末と反応してMgOまたはマグネシウム−ホウ素−複合酸化物を形成する可能性が高い。 The present invention relates to this final step. During the heat treatment step, any free oxygen in the furnace is likely to react with the magnesium powder to form MgO or magnesium-boron-complex oxide.
したがって、本発明は、添付の特許請求の範囲で規定されるような、MgB2導体間に超伝導接合部を準備するための方法に関する。 The present invention therefore relates to a method for preparing a superconducting junction between MgB 2 conductors, as defined in the appended claims.
本発明は、添付の請求項で規定されるように、接合部が形成される間、酸素が炉内の環境から効果的に除去される、MgB2導体間に接合部を形成するための方法を提供する。 The present invention provides a method for forming a joint between MgB 2 conductors, wherein oxygen is effectively removed from the environment within the furnace while the joint is formed, as defined in the appended claims. I will provide a.
本発明の方法によると、接合部が形成される間、チタンが、好ましくはペレットの形で、炉内に提供される。チタンは、酸素のゲッターとしての役割を果たし、炉中に存在することもあるどんな酸素も、マグネシウムと反応するよりもむしろ、チタンによって優先的に捕捉されて酸化チタンになる。チタンは、酸素が接合部から迅速にかつ効果的に除去されるように、接合モールドに近接して置かれる。チタンによる遊離酸素の捕捉は、酸化マグネシウムによる接合部のどんな汚染も回避し、背景磁界強度および電流密度に容認できるほど耐性がある持続的MgB2接合部につながる。 According to the method of the present invention, titanium is provided into the furnace, preferably in the form of pellets, while the joint is formed. Titanium serves as an oxygen getter and any oxygen that may be present in the furnace is preferentially trapped by the titanium into titanium oxide rather than reacting with magnesium. Titanium is placed in close proximity to the joining mold so that oxygen can be quickly and effectively removed from the joint. The capture of free oxygen by titanium avoids any contamination of the junction by magnesium oxide and leads to a persistent MgB 2 junction that is acceptable to background magnetic field strength and current density.
本方法での残りの段階は、変わらない。本発明の方法は、機械的圧力が接合プロセスの間維持される配置で、または機械的圧力が接合の間解放される配置で適用されてもよい。 The remaining steps in the method remain unchanged. The method of the present invention may be applied in an arrangement where mechanical pressure is maintained during the bonding process or in an arrangement where mechanical pressure is released during the bonding.
炉は、好ましくは10−7bar(0.01Pa)程度まで真空ポンプによって排気されてもよく、またはチタンによって捕捉される必要のある酸素の量を低減するために不活性フラッシュ装置を提供されてもよい。 The furnace may be evacuated by a vacuum pump, preferably to the order of 10 −7 bar (0.01 Pa), or provided with an inert flash device to reduce the amount of oxygen that needs to be trapped by titanium. Also good.
したがって、本発明は、MgB2ワイヤの接合のためにMgB2形成を実現するためのマグネシウムおよびホウ素粉末の熱処理の間に存在することもあるどんな酸素も捕獲するためにチタンペレットの使用を提供する。好ましくは、高真空ポンプが、炉を排気するために提供され、これは、酸素のいくらかを除去することになる。残りの酸素は、チタンによって優先的に捕捉されることになり、酸化マグネシウムの形成を回避する。 Thus, the present invention provides the use of titanium pellets to capture any oxygen that may be present during the heat treatment of magnesium and boron powders to achieve MgB 2 formation for bonding MgB 2 wires . Preferably, a high vacuum pump is provided to evacuate the furnace, which will remove some of the oxygen. The remaining oxygen will be preferentially captured by titanium, avoiding the formation of magnesium oxide.
MgB2フィラメント間に十分な接合部を作ることは、困難であることが分かっている。接合部は、動作温度においてさえ超伝導にならないか、または接合部は、容認できないほど低い背景磁界強度においてもしくは容認できないほど低いしきいを超える電流が通されるときに抵抗性になる(「クエンチ現象」として知られている)。
MgB 2 ワイヤを接合するための周知の方法は、「Li et al.; “High critical current joint of MgB 2 tapes using Mg and B powder mixture as flux”; Superconductor Science Technology; Vol.21; No.2; 25017 2008-02-01 pp.1-5; ISSN:0953-2048; XP020128600」において記載されている。
Producing sufficient joints between MgB 2 filaments has proven difficult. The junction does not become superconducting even at operating temperatures, or the junction becomes resistive when a current is passed at an unacceptably low background magnetic field strength or above an unacceptably low threshold ("quenching" Known as "phenomenon").
Well-known methods for joining MgB 2 wires are described in “Li et al .;“ High critical current joint of MgB 2 tapes using Mg and B powder mixture as flux ”; Superconductor Science Technology; Vol. 21; 25017 2008-02-01 pp.1-5; ISSN: 0953-2048; XP020128600 ".
Claims (3)
炉中で前記MgB2フィラメントをマグネシウム粉末およびホウ素粉末の混合物にさらすステップと、
前記MgB2フィラメントならびに前記マグネシウムおよびホウ素粉末を一緒に540℃を超えるまたは540℃程度の温度で圧縮するステップとを含む、超伝導ワイヤのMgB2フィラメント間に接合部を形成するための方法であって、
チタンが、前記炉内に提供されて、前記炉内に存在する酸素を優先的に捕捉することを特徴とする、方法。 Exposing the MgB 2 filament from the wires to be joined;
Exposing the MgB 2 filament in a furnace to a mixture of magnesium powder and boron powder;
Compressing the MgB 2 filament and the magnesium and boron powder together at a temperature above 540 ° C. or at a temperature on the order of 540 ° C. to form a joint between the MgB 2 filaments of a superconducting wire. And
Titanium is provided in the furnace to preferentially capture oxygen present in the furnace.
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PCT/EP2012/072869 WO2013107537A1 (en) | 2012-01-20 | 2012-11-16 | Methods for forming joints between magnesium diboride conductors |
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GB2498565B (en) * | 2012-01-20 | 2014-09-17 | Siemens Plc | Methods for forming joints between magnesium diboride conductors |
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KR20200103369A (en) * | 2019-02-25 | 2020-09-02 | 강원대학교산학협력단 | Joint Structure of Single Core Superconducting Cables And Manufacturing Method Thereof |
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KR20220046084A (en) * | 2020-10-07 | 2022-04-14 | 강원대학교산학협력단 | Joint Structure of Multi-filament Core Superconducting Wire And Manufacturing Method Thereof |
KR102429818B1 (en) | 2020-10-07 | 2022-08-05 | 강원대학교산학협력단 | Joint Structure of Multi-filament Core Superconducting Wire And Manufacturing Method Thereof |
Also Published As
Publication number | Publication date |
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GB2498565A (en) | 2013-07-24 |
US9837190B2 (en) | 2017-12-05 |
US20140364318A1 (en) | 2014-12-11 |
KR20140116529A (en) | 2014-10-02 |
EP2805362B1 (en) | 2016-12-28 |
CN104040744B (en) | 2017-06-16 |
WO2013107537A1 (en) | 2013-07-25 |
GB201200989D0 (en) | 2012-03-07 |
GB2498565B (en) | 2014-09-17 |
CN104040744A (en) | 2014-09-10 |
JP6162148B2 (en) | 2017-07-12 |
KR101898644B1 (en) | 2018-10-04 |
EP2805362A1 (en) | 2014-11-26 |
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